title: Diffusion and interfacial transport of water in Nafion.
abstract: Water absorption, membrane swelling, and self-diffusivity of water in 1100 equivalent weight Nafion were measured as functions of temperature and water activity. Free volume per water at 80 °C, determined from water uptake and volume expansion data, decreases with water content in the membrane from 12 cm(3)/mol at λ = 0.5 H(2)O/SO(3) to 1.5 cm(3)/mol at λ = 4. The change in free volume with water content displays a transition at λ = 4. Limiting water self-diffusivity in Nafion was determined by pulsed gradient spin echo NMR at long delay times. The limiting self-diffusivity increases exponentially with water activity; the rate of increase of diffusivity with water content shows a transition at λ = 4. The tortuosity of the hydrophilic domains in Nafion decreased from 20 at low membrane water activity to 3 at λ = 4. It suggested a change in the connectivity of the hydrophilic domains absorbed water occurs at λ ∼ 4. The diffusivity results were employed to separate the contributions of diffusional and interfacial resistance for water transport across Nafion membranes, which enabled the determination of the interfacial mass transport coefficients. A diffusion model was developed which incorporated activity-dependent diffusivity, volume expansion, and the interfacial resistance, and was used to resolve the water activity profiles in the membrane.
authors.affiliation: Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA.
authors.forename: Qiao
authors.initials: Q
authors.lastname: Zhao
authors.forename: Paul
authors.initials: P
authors.lastname: Majsztrik
authors.forename: Jay
authors.initials: J
authors.lastname: Benziger